[2-(Isopropylthio)benzoato-O,S]phenyl(triphenylphosphine)palladium(II) tetrahydrofuran solvate

In the title compound, [Pd(C₆H₅)(C₁₀H₁₁O₂S)(C₁₈H₁₅P)]·C₄H₈O, an iso­propyl­thio­benzoate ligand is coordinated in a bidentate fashion to the central Pd atom through the O and S atoms. The square-planar geometry of the Pd atom is completed by a phenyl ligand and a tri­phenyl­phosphine group but is distorted by the bidentate ligand, which forms a six-membered chelate ring. This ring deviates strongly from planarity, which is illustrated by the plane through the phenyl portion of the chelate ring forming a dihedral angle of 62.3 (1)° with the coordination plane.

S1. Comment

The title compound, (I), was synthesized for its potential catalytic properties in C—C linkage reactions, such as the oligomerization of ethene. P—O hemilabile ligands coordinated to Ni are well known in such reactions, and the catalytic mechanism proposed by Rauchfuss et al. (1975) can also be applied to S—O hemilabile ligands. The hemilabile ligand may be either monodentate (coordinated only through the O) or bidentate (coordinated through both S and O). In the presence of a substrate molecule the S of the complex containing the bidentate ligand will decoordinate leaving a vacant coordination site. Since the hemilabile ligand is still bound to the Pd through the O, the S atom is close enough to recoordinate to the Pd once the catalytic reaction has taken place. \scheme

The synthesis and characterization of a series of Pd complexes containing potentially hemilabile S—O ligands, of the type trans-[Pd(OOC-C₆H₄-2-SR-κO)(C₆H₅){P(C₆H₅)₃}₂], have previously been reported [R = Et was described by Meyer et al., (1998), while the two conformational isomers of R = Me were discussed by Kruger et al. (2000)]. Although the hemilability of the complexes has been proven in solution, all the previously reported crystal structures were of the monodentate form. This paper presents the first example of a crystal structure of a Pd complex with bidentate coordination of the S—O ligand, through both the S and O atoms.

The molecular structure and atom-numbering scheme for (I) are shown in Fig. 1. The majority of the bond lengths and angles agree with those found in the previously determined ethylthiobenzoate and methylthiobenzoate structures, although the Pd—P bond length of 2.279 (1) Å is shorter. This suggests that the trans influence of the S is smaller than that of P (the trans ligand in the previously determined structures).

The conformation of the chelate ring agrees with the findings of Corey & Bailar (1959). They determined that enhanced puckering of a six-membered ring occurred when a metal-N bond distance was greater than 2 Å and the bite-angle of the chelate was close to 90°. This increased the interactions of cis substituents, thus destabilizing the ring, particularly when bulky substituents were present. This is clearly the case in the present structure, where the bond angle is close to 90° and the chelate ring is extremely buckled, whereas the previous monodentate methylthiobenzoate and ethylthiobenzoate ligands were planar. The extent of the puckering is illustrated by the phenyl portion of the ligand (C42—C47), which is tilted at an angle of 62.3 (1)° to the molecular plane containing the Pd, and by the deviations from 0 or 180° in the torsion angles shown in Table 1.

Although the bond angles around the Pd do not deviate substantially from the expected 90 and 180°, the planarity of the square-planar conformation around the Pd is affected by the puckered ligand, giving a tetrahedral distortion. A calculation of the best plane through the Pd and the four atoms bonded to it showed that the Pd lies only 0.009 (1) Å above the plane, whereas the trans C31 and O41 lie 0.173 (2) and 0.180 (2) Å, respectively, above the plane and the P and S lie 0.182 (1) and 0.181 (1) Å, respectively, below the plane.

S2. Experimental

Thallium 2-isopropylthiobenzoate was obtained by stirring thallium carbonate with the stoichiometric amount of 2-isopropylthiobenzoic acid in methanol at ca 313 K for 30 min and removing the solvent in vacuo. The salt was then added in 20% excess to a solution of [Pd(tmeda)(C₆H₅)I] (tmeda = tetramethylethylenediamine) in tetrahydrofuran (THF) and the mixture stirred for 1 h at room temperature. A solution of the stoichiometric amount of triphenylphosphine in THF was added dropwise to the suspension over a period of 1 h. After stirring overnight the precipitated thallium iodide was removed by filtration through Celite. The volume of the solution was reduced to one third and layered with n-pentane. Single crystals of (I) were obtained at room temperature in a yield of 30% with no further crystallization.

S3. Refinement

The THF molecule was found to be disordered. This was resolved by a rigid body refinement of an ideal molecule, which showed that the disorder could be described by three different conformations in the ratio 40:27:33. Each conformation was refined with common isotropic displacement parameters.

Computing details

Data collection: SMART (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEX (McArdle, 1995); software used to prepare material for publication: SHELXL97.

Figures

Fig. 1. The molecular conformation of (I) showing the atom-numbering scheme and the disordered solvent. Displacement ellipsoids are shown at the 50% probability level and H atoms are drawn as spheres of arbitrary radii.

[(2-isopropylthio)benzoato-O,S]phenyl(triphenylphosphine)palladium(II) tetrahydrofuran solvate

Crystal data

[Pd(C10H11O2S)(C6H5)(C18H15P)]·C4H8O	Z = 2
Mr = 713.12	F(000) = 736
Triclinic, P1	Dx = 1.369 Mg m^−3
a = 9.8574 (6) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.9503 (6) Å	Cell parameters from 7829 reflections
c = 16.5057 (10) Å	θ = 1.3–25.0°
α = 100.142 (1)°	µ = 0.68 mm^−1
β = 95.803 (1)°	T = 293 K
γ = 96.244 (1)°	Prism, colourless
V = 1730.2 (2) Å^3	0.30 × 0.25 × 0.20 mm

Data collection

Siemens SMART CCD area detector diffractometer	5613 independent reflections
Radiation source: fine-focus sealed tube	5028 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.017
ω scans	θmax = 25.0°, θmin = 1.3°
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	h = −11→11
Tmin = 0.82, Tmax = 0.87	k = −10→13
7829 measured reflections	l = −19→19

Refinement

Refinement on F^2	Primary atom site location: patterson
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.097	H-atom parameters constrained
S = 1.10	w = 1/[σ^2(Fo^2) + (0.0318P)^2 + 2.4317P] where P = (Fo^2 + 2Fc^2)/3
5613 reflections	(Δ/σ)max = 0.019
386 parameters	Δρmax = 0.66 e Å^−3
1 restraint	Δρmin = −0.50 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Equation of least-squares plane through Pd, C31, O41, S and P: - 5.9973 (0.0075) x + 9.3474 (0.0050) y - 2.2261 (0.0168) z = 1.7945(0.0061) Deviations of atoms from least-squares plane (* indicates included in calculation) * 0.0093 (0.0011) Pd * 0.1802 (0.0016) C31 * 0.1732 (0.0015) O41 * -0.1817 (0.0011) S * -0.1810 (0.0011) P

Rms deviation of fitted atoms = 0.1602

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement.

The structure was solved by interpretation of a Patterson synthesis which yielded the position of the metal atom, while the remaining non-metal atoms were found from the difference Fourier maps. The H atoms could be located by difference Fourier, but were refined in ideal positions with bond lengths of 0.93 Å for aromatic C—H bonds, 0.98 Å for the tertiary C—H bond and 0.96 Å for the rest, and with displacement parameters 1.2 times that of the atom on which they were riding.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Pd	0.60081 (3)	0.75046 (3)	0.722268 (17)	0.03841 (10)
P	0.76178 (9)	0.85819 (8)	0.82645 (6)	0.0360 (2)
S	0.45320 (11)	0.61017 (9)	0.61663 (6)	0.0473 (2)
O41	0.4665 (3)	0.7017 (2)	0.80562 (16)	0.0495 (7)
O42	0.3153 (4)	0.5801 (3)	0.8552 (2)	0.0755 (10)
C41	0.4007 (4)	0.5951 (4)	0.8078 (2)	0.0480 (10)
C42	0.4270 (4)	0.4801 (4)	0.7481 (2)	0.0483 (10)
C43	0.4295 (5)	0.3691 (4)	0.7782 (3)	0.0632 (12)
H43	0.4185	0.3696	0.8336	0.076*
C44	0.4475 (6)	0.2592 (4)	0.7289 (4)	0.0772 (15)
H44	0.4523	0.1874	0.7512	0.093*
C45	0.4586 (6)	0.2553 (4)	0.6461 (3)	0.0753 (14)
H45	0.4682	0.1802	0.6122	0.090*
C46	0.4555 (5)	0.3627 (4)	0.6132 (3)	0.0625 (12)
H46	0.4616	0.3598	0.5571	0.075*
C47	0.4432 (4)	0.4755 (3)	0.6646 (2)	0.0454 (9)
C51	0.2805 (5)	0.6577 (4)	0.6177 (3)	0.0581 (11)
H51	0.2586	0.6749	0.6749	0.057 (12)*
C52	0.2845 (6)	0.7765 (5)	0.5823 (4)	0.0785 (15)
H521	0.1968	0.8069	0.5836	0.095 (19)*
H522	0.3047	0.7591	0.5260	0.084 (18)*
H523	0.3544	0.8387	0.6147	0.078 (16)*
C53	0.1753 (6)	0.5546 (6)	0.5663 (5)	0.098 (2)
H531	0.1858	0.4772	0.5845	0.11 (2)*
H532	0.1892	0.5460	0.5089	0.13 (3)*
H533	0.0845	0.5754	0.5729	0.12 (2)*
C31	0.7046 (4)	0.8153 (4)	0.6382 (2)	0.0469 (9)
C32	0.8022 (5)	0.7541 (5)	0.5991 (3)	0.0614 (12)
H32	0.8267	0.6810	0.6145	0.074*
C33	0.8645 (6)	0.8008 (7)	0.5365 (3)	0.0875 (18)
H33	0.9303	0.7588	0.5106	0.105*
C34	0.8292 (8)	0.9077 (8)	0.5133 (4)	0.103 (2)
H34	0.8718	0.9393	0.4722	0.123*
C35	0.7314 (8)	0.9686 (6)	0.5504 (4)	0.098 (2)
H35	0.7057	1.0402	0.5334	0.118*
C36	0.6702 (5)	0.9238 (5)	0.6133 (3)	0.0702 (14)
H36	0.6054	0.9671	0.6391	0.084*
C111	0.7117 (4)	1.0047 (3)	0.8766 (2)	0.0407 (8)
C112	0.8047 (5)	1.1093 (4)	0.9138 (3)	0.0601 (12)
H112	0.8979	1.1096	0.9090	0.072*
C113	0.7581 (6)	1.2125 (4)	0.9579 (3)	0.0755 (15)
H113	0.8206	1.2820	0.9829	0.091*
C114	0.6217 (7)	1.2137 (5)	0.9653 (3)	0.0751 (15)
H114	0.5914	1.2837	0.9951	0.090*
C115	0.5297 (6)	1.1117 (5)	0.9288 (3)	0.0765 (15)
H115	0.4368	1.1123	0.9343	0.092*
C116	0.5736 (5)	1.0080 (4)	0.8840 (3)	0.0583 (11)
H116	0.5099	0.9397	0.8585	0.070*
C121	0.9402 (4)	0.8938 (3)	0.8071 (2)	0.0417 (9)
C122	1.0435 (4)	0.8344 (4)	0.8389 (3)	0.0523 (10)
H122	1.0230	0.7758	0.8718	0.063*
C123	1.1779 (5)	0.8606 (5)	0.8227 (3)	0.0699 (13)
H123	1.2471	0.8202	0.8446	0.084*
C124	1.2072 (5)	0.9462 (5)	0.7742 (3)	0.0716 (14)
H124	1.2972	0.9644	0.7633	0.086*
C125	1.1057 (5)	1.0061 (5)	0.7413 (3)	0.0676 (13)
H125	1.1270	1.0641	0.7081	0.081*
C126	0.9722 (4)	0.9804 (4)	0.7575 (3)	0.0543 (10)
H126	0.9035	1.0210	0.7352	0.065*
C131	0.7733 (4)	0.7668 (3)	0.9089 (2)	0.0400 (8)
C132	0.8075 (4)	0.8223 (4)	0.9913 (2)	0.0507 (10)
H132	0.8256	0.9090	1.0064	0.061*
C133	0.8148 (5)	0.7488 (5)	1.0513 (3)	0.0660 (13)
H133	0.8386	0.7866	1.1067	0.079*
C134	0.7877 (5)	0.6218 (5)	1.0304 (3)	0.0734 (14)
H134	0.7927	0.5730	1.0711	0.088*
C135	0.7530 (6)	0.5669 (5)	0.9488 (4)	0.0790 (16)
H135	0.7345	0.4802	0.9343	0.095*
C136	0.7450 (5)	0.6383 (4)	0.8877 (3)	0.0626 (12)
H136	0.7206	0.5998	0.8324	0.075*
O61	1.0980 (15)	0.6298 (16)	0.3639 (8)	0.152 (4)*	0.402 (4)
C61	1.013 (2)	0.6997 (15)	0.3359 (10)	0.152 (4)*	0.402 (4)
H61A	1.0569	0.7855	0.3439	0.183*	0.402 (4)
H61B	0.9323	0.6983	0.3646	0.183*	0.402 (4)
C62	0.978 (2)	0.6515 (18)	0.2526 (12)	0.152 (4)*	0.402 (4)
H62A	1.0409	0.6884	0.2195	0.183*	0.402 (4)
H62B	0.8849	0.6644	0.2341	0.183*	0.402 (4)
C63	0.989 (2)	0.5250 (18)	0.2493 (12)	0.152 (4)*	0.402 (4)
H63A	0.9059	0.4809	0.2628	0.183*	0.402 (4)
H63B	1.0080	0.4854	0.1950	0.183*	0.402 (4)
C64	1.0985 (18)	0.5293 (17)	0.3089 (11)	0.152 (4)*	0.402 (4)
H64A	1.0888	0.4559	0.3342	0.183*	0.402 (4)
H64B	1.1840	0.5324	0.2845	0.183*	0.402 (4)
O62	1.1878 (18)	0.6391 (17)	0.2557 (12)	0.133 (6)*	0.272 (9)
C65	1.057 (2)	0.612 (2)	0.2115 (13)	0.133 (6)*	0.272 (9)
H65A	1.0390	0.5241	0.1856	0.159*	0.272 (9)
H65B	1.0485	0.6617	0.1685	0.159*	0.272 (9)
C66	0.959 (3)	0.642 (2)	0.2716 (15)	0.133 (6)*	0.272 (9)
H66A	0.9306	0.5708	0.2963	0.159*	0.272 (9)
H66B	0.8778	0.6702	0.2459	0.159*	0.272 (9)
C67	1.042 (3)	0.745 (2)	0.3342 (14)	0.133 (6)*	0.272 (9)
H67A	1.0398	0.8255	0.3172	0.159*	0.272 (9)
H67B	1.0103	0.7501	0.3883	0.159*	0.272 (9)
C68	1.181 (2)	0.706 (2)	0.3347 (13)	0.133 (6)*	0.272 (9)
H68A	1.2505	0.7791	0.3477	0.159*	0.272 (9)
H68B	1.1960	0.6546	0.3760	0.159*	0.272 (9)
O63	1.1887 (17)	0.6006 (18)	0.3255 (10)	0.143 (5)*	0.325 (9)
C69	1.122 (2)	0.5059 (18)	0.2695 (13)	0.143 (5)*	0.325 (9)
H69A	1.0871	0.4387	0.2962	0.171*	0.325 (9)
H69B	1.1820	0.4738	0.2303	0.171*	0.325 (9)
C610	1.012 (2)	0.553 (2)	0.2287 (14)	0.143 (5)*	0.325 (9)
H61C	0.9304	0.5451	0.2566	0.171*	0.325 (9)
H61D	0.9903	0.5097	0.1714	0.171*	0.325 (9)
C611	1.066 (2)	0.6800 (19)	0.2342 (15)	0.143 (5)*	0.325 (9)
H61E	1.1223	0.6901	0.1903	0.171*	0.325 (9)
H61F	0.9934	0.7328	0.2322	0.171*	0.325 (9)
C612	1.146 (2)	0.7068 (17)	0.3123 (12)	0.143 (5)*	0.325 (9)
H61G	1.2236	0.7694	0.3129	0.171*	0.325 (9)
H61H	1.0910	0.7383	0.3551	0.171*	0.325 (9)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pd	0.04090 (17)	0.03779 (16)	0.03584 (17)	−0.00140 (11)	0.00478 (12)	0.00903 (11)
P	0.0375 (5)	0.0325 (5)	0.0381 (5)	0.0026 (4)	0.0036 (4)	0.0090 (4)
S	0.0558 (6)	0.0485 (5)	0.0346 (5)	−0.0055 (4)	0.0045 (4)	0.0080 (4)
O41	0.0567 (17)	0.0472 (15)	0.0424 (15)	−0.0061 (13)	0.0150 (13)	0.0048 (12)
O42	0.100 (3)	0.063 (2)	0.067 (2)	−0.0080 (18)	0.046 (2)	0.0140 (16)
C41	0.058 (3)	0.048 (2)	0.039 (2)	−0.0006 (19)	0.009 (2)	0.0133 (17)
C42	0.050 (2)	0.048 (2)	0.046 (2)	−0.0046 (18)	0.0065 (19)	0.0135 (18)
C43	0.076 (3)	0.058 (3)	0.060 (3)	0.003 (2)	0.013 (2)	0.023 (2)
C44	0.101 (4)	0.049 (3)	0.084 (4)	0.009 (3)	0.013 (3)	0.021 (3)
C45	0.094 (4)	0.044 (3)	0.084 (4)	0.013 (2)	0.009 (3)	0.001 (2)
C46	0.074 (3)	0.056 (3)	0.054 (3)	0.004 (2)	0.007 (2)	0.003 (2)
C47	0.048 (2)	0.043 (2)	0.044 (2)	−0.0010 (17)	0.0029 (18)	0.0085 (17)
C51	0.056 (3)	0.063 (3)	0.054 (3)	0.002 (2)	−0.005 (2)	0.017 (2)
C52	0.084 (4)	0.070 (3)	0.084 (4)	0.012 (3)	−0.003 (3)	0.029 (3)
C53	0.076 (4)	0.087 (4)	0.115 (6)	−0.014 (3)	−0.033 (4)	0.021 (4)
C31	0.047 (2)	0.049 (2)	0.043 (2)	−0.0052 (18)	0.0023 (19)	0.0143 (17)
C32	0.058 (3)	0.076 (3)	0.047 (3)	−0.005 (2)	0.013 (2)	0.008 (2)
C33	0.068 (3)	0.129 (5)	0.057 (3)	−0.022 (3)	0.023 (3)	0.004 (3)
C34	0.102 (5)	0.136 (6)	0.066 (4)	−0.047 (5)	0.005 (4)	0.049 (4)
C35	0.106 (5)	0.099 (5)	0.095 (5)	−0.021 (4)	0.000 (4)	0.065 (4)
C36	0.075 (3)	0.067 (3)	0.076 (3)	−0.002 (2)	0.009 (3)	0.039 (3)
C111	0.045 (2)	0.0357 (19)	0.043 (2)	0.0073 (16)	0.0032 (17)	0.0097 (16)
C112	0.057 (3)	0.043 (2)	0.076 (3)	0.0032 (19)	−0.003 (2)	0.006 (2)
C113	0.100 (4)	0.039 (2)	0.078 (3)	0.007 (2)	−0.015 (3)	0.001 (2)
C114	0.115 (5)	0.053 (3)	0.063 (3)	0.034 (3)	0.019 (3)	0.006 (2)
C115	0.077 (4)	0.068 (3)	0.092 (4)	0.029 (3)	0.031 (3)	0.009 (3)
C116	0.056 (3)	0.054 (2)	0.064 (3)	0.009 (2)	0.009 (2)	0.006 (2)
C121	0.039 (2)	0.041 (2)	0.043 (2)	0.0001 (16)	0.0040 (17)	0.0044 (16)
C122	0.045 (2)	0.056 (2)	0.058 (3)	0.0128 (19)	0.008 (2)	0.014 (2)
C123	0.045 (3)	0.084 (3)	0.084 (4)	0.020 (2)	0.012 (2)	0.015 (3)
C124	0.049 (3)	0.090 (4)	0.074 (3)	−0.003 (3)	0.019 (3)	0.013 (3)
C125	0.061 (3)	0.073 (3)	0.064 (3)	−0.017 (2)	0.010 (2)	0.016 (2)
C126	0.044 (2)	0.058 (3)	0.062 (3)	−0.0015 (19)	0.004 (2)	0.019 (2)
C131	0.0350 (19)	0.043 (2)	0.045 (2)	0.0038 (15)	0.0067 (16)	0.0159 (16)
C132	0.054 (2)	0.052 (2)	0.047 (2)	0.0049 (19)	0.007 (2)	0.0128 (18)
C133	0.071 (3)	0.090 (4)	0.044 (2)	0.016 (3)	0.009 (2)	0.025 (2)
C134	0.080 (4)	0.081 (4)	0.074 (4)	0.012 (3)	0.017 (3)	0.052 (3)
C135	0.099 (4)	0.050 (3)	0.093 (4)	0.002 (3)	0.000 (3)	0.035 (3)
C136	0.085 (3)	0.040 (2)	0.061 (3)	0.005 (2)	−0.004 (2)	0.013 (2)

Geometric parameters (Å, º)

Pd—C31	1.988 (4)	C123—C124	1.362 (7)
Pd—O41	2.098 (3)	C123—H123	0.9300
Pd—P	2.2788 (10)	C124—C125	1.373 (7)
Pd—S	2.3611 (10)	C124—H124	0.9300
P—C131	1.828 (4)	C125—C126	1.378 (6)
P—C111	1.814 (4)	C125—H125	0.9300
P—C121	1.831 (4)	C126—H126	0.9300
S—C47	1.791 (4)	C131—C136	1.379 (5)
S—C51	1.835 (5)	C131—C132	1.380 (5)
O41—C41	1.281 (5)	C132—C133	1.383 (6)
O42—C41	1.223 (5)	C132—H132	0.9300
C41—C42	1.519 (6)	C133—C134	1.363 (7)
C42—C47	1.397 (5)	C133—H133	0.9300
C42—C43	1.394 (6)	C134—C135	1.367 (7)
C43—C44	1.369 (7)	C134—H134	0.9300
C43—H43	0.9300	C135—C136	1.383 (6)
C44—C45	1.374 (7)	C135—H135	0.9300
C44—H44	0.9300	C136—H136	0.9300
C45—C46	1.381 (6)	O61—C61	1.297 (12)
C45—H45	0.9300	O61—C64	1.298 (12)
C46—C47	1.393 (6)	C61—C62	1.377 (13)
C46—H46	0.9300	C61—H61A	0.9700
C51—C53	1.516 (7)	C61—H61B	0.9700
C51—C52	1.516 (6)	C62—C63	1.393 (13)
C51—H51	0.9800	C62—H62A	0.9700
C52—H521	0.9600	C62—H62B	0.9700
C52—H522	0.9600	C63—C64	1.377 (13)
C52—H523	0.9600	C63—H63A	0.9700
C53—H531	0.9600	C63—H63B	0.9700
C53—H532	0.9600	C64—H64A	0.9700
C53—H533	0.9600	C64—H64B	0.9700
C31—C32	1.381 (6)	O62—C65	1.392 (17)
C31—C36	1.388 (6)	O62—C68	1.392 (17)
C32—C33	1.397 (7)	C65—C66	1.477 (18)
C32—H32	0.9300	C65—H65A	0.9700
C33—C34	1.363 (9)	C65—H65B	0.9700
C33—H33	0.9300	C66—C67	1.495 (18)
C34—C35	1.365 (10)	C66—H66A	0.9700
C34—H34	0.9300	C66—H66B	0.9700
C35—C36	1.387 (7)	C67—C68	1.477 (18)
C35—H35	0.9300	C67—H67A	0.9700
C36—H36	0.9300	C67—H67B	0.9700
C111—C116	1.382 (6)	C68—H68A	0.9700
C111—C112	1.393 (5)	C68—H68B	0.9700
C112—C113	1.381 (6)	O63—C612	1.325 (15)
C112—H112	0.9300	O63—C69	1.325 (15)
C113—C114	1.364 (8)	C69—C610	1.405 (16)
C113—H113	0.9300	C69—H69A	0.9700
C114—C115	1.365 (7)	C69—H69B	0.9700
C114—H114	0.9300	C610—C611	1.423 (16)
C115—C116	1.379 (6)	C610—H61C	0.9700
C115—H115	0.9300	C610—H61D	0.9700
C116—H116	0.9300	C611—C612	1.406 (16)
C121—C122	1.375 (5)	C611—H61E	0.9700
C121—C126	1.390 (5)	C611—H61F	0.9700
C122—C123	1.387 (6)	C612—H61G	0.9700
C122—H122	0.9300	C612—H61H	0.9700
C31—Pd—O41	170.24 (14)	C123—C124—H124	119.6
C31—Pd—P	90.77 (11)	C125—C124—H124	119.6
O41—Pd—P	92.60 (8)	C124—C125—C126	120.0 (5)
C31—Pd—S	90.71 (11)	C124—C125—H125	120.0
O41—Pd—S	87.47 (8)	C126—C125—H125	120.0
P—Pd—S	170.55 (4)	C125—C126—C121	120.0 (4)
C131—P—C111	103.81 (17)	C125—C126—H126	120.0
C131—P—C121	104.26 (17)	C121—C126—H126	120.0
C111—P—C121	106.13 (17)	C136—C131—C132	119.3 (4)
C131—P—Pd	107.90 (12)	C136—C131—P	118.6 (3)
C111—P—Pd	112.97 (12)	C132—C131—P	122.1 (3)
C121—P—Pd	120.26 (12)	C133—C132—C131	119.8 (4)
C47—S—C51	103.8 (2)	C133—C132—H132	120.1
C47—S—Pd	98.71 (13)	C131—C132—H132	120.1
C51—S—Pd	107.62 (15)	C134—C133—C132	121.0 (4)
C41—O41—Pd	129.4 (3)	C134—C133—H133	119.5
O42—C41—O41	123.4 (4)	C132—C133—H133	119.5
O42—C41—C42	117.3 (4)	C133—C134—C135	119.2 (4)
O41—C41—C42	119.3 (4)	C133—C134—H134	120.4
C47—C42—C43	117.3 (4)	C135—C134—H134	120.4
C47—C42—C41	125.2 (3)	C134—C135—C136	121.0 (5)
C43—C42—C41	117.4 (4)	C134—C135—H135	119.5
C44—C43—C42	122.0 (5)	C136—C135—H135	119.5
C44—C43—H43	119.0	C131—C136—C135	119.7 (4)
C42—C43—H43	119.0	C131—C136—H136	120.1
C45—C44—C43	119.9 (5)	C135—C136—H136	120.1
C45—C44—H44	120.1	C61—O61—C64	109.8
C43—C44—H44	120.1	O61—C61—C62	106.7
C44—C45—C46	120.2 (5)	O61—C61—H61A	110.4
C44—C45—H45	119.9	C62—C61—H61A	110.4
C46—C45—H45	119.9	O61—C61—H61B	110.4
C45—C46—C47	119.7 (4)	C62—C61—H61B	110.4
C45—C46—H46	120.1	H61A—C61—H61B	108.6
C47—C46—H46	120.1	C61—C62—C63	101.9
C42—C47—C46	120.8 (4)	C61—C62—H62A	111.4
C42—C47—S	123.6 (3)	C63—C62—H62A	111.4
C46—C47—S	115.6 (3)	C61—C62—H62B	111.4
C53—C51—C52	111.4 (4)	C63—C62—H62B	111.4
C53—C51—S	109.9 (4)	H62A—C62—H62B	109.2
C52—C51—S	106.4 (3)	C64—C63—C62	101.9
C53—C51—H51	109.7	C64—C63—H63A	111.4
C52—C51—H51	109.7	C62—C63—H63A	111.4
S—C51—H51	109.7	C64—C63—H63B	111.4
C51—C52—H521	109.5	C62—C63—H63B	111.4
C51—C52—H522	109.5	H63A—C63—H63B	109.3
H521—C52—H522	109.5	O61—C64—C63	106.7
C51—C52—H523	109.5	O61—C64—H64A	110.4
H521—C52—H523	109.5	C63—C64—H64A	110.4
H522—C52—H523	109.5	O61—C64—H64B	110.4
C51—C53—H531	109.5	C63—C64—H64B	110.4
C51—C53—H532	109.5	H64A—C64—H64B	108.6
H531—C53—H532	109.5	C65—O62—C68	109.8
C51—C53—H533	109.5	O62—C65—C66	106.8
H531—C53—H533	109.5	O62—C65—H65A	110.4
H532—C53—H533	109.5	C66—C65—H65A	110.4
C32—C31—C36	118.1 (4)	O62—C65—H65B	110.4
C32—C31—Pd	123.7 (3)	C66—C65—H65B	110.4
C36—C31—Pd	118.1 (3)	H65A—C65—H65B	108.6
C31—C32—C33	120.7 (5)	C65—C66—C67	101.9
C31—C32—H32	119.7	C65—C66—H66A	111.4
C33—C32—H32	119.7	C67—C66—H66A	111.4
C34—C33—C32	120.1 (6)	C65—C66—H66B	111.4
C34—C33—H33	119.9	C67—C66—H66B	111.4
C32—C33—H33	119.9	H66A—C66—H66B	109.3
C33—C34—C35	120.1 (5)	C68—C67—C66	101.9
C33—C34—H34	119.9	C68—C67—H67A	111.4
C35—C34—H34	119.9	C66—C67—H67A	111.4
C34—C35—C36	120.2 (6)	C68—C67—H67B	111.4
C34—C35—H35	119.9	C66—C67—H67B	111.4
C36—C35—H35	119.9	H67A—C67—H67B	109.3
C31—C36—C35	120.9 (6)	O62—C68—C67	106.7
C31—C36—H36	119.6	O62—C68—H68A	110.4
C35—C36—H36	119.6	C67—C68—H68A	110.4
C116—C111—C112	118.6 (4)	O62—C68—H68B	110.4
C116—C111—P	117.3 (3)	C67—C68—H68B	110.4
C112—C111—P	123.9 (3)	H68A—C68—H68B	108.6
C111—C112—C113	119.9 (5)	C612—O63—C69	109.8
C111—C112—H112	120.1	O63—C69—C610	106.8
C113—C112—H112	120.1	O63—C69—H69A	110.4
C114—C113—C112	120.8 (5)	C610—C69—H69A	110.4
C114—C113—H113	119.6	O63—C69—H69B	110.4
C112—C113—H113	119.6	C610—C69—H69B	110.4
C115—C114—C113	119.7 (5)	H69A—C69—H69B	108.6
C115—C114—H114	120.1	C69—C610—C611	101.9
C113—C114—H114	120.1	C69—C610—H61C	111.4
C114—C115—C116	120.5 (5)	C611—C610—H61C	111.4
C114—C115—H115	119.7	C69—C610—H61D	111.4
C116—C115—H115	119.7	C611—C610—H61D	111.4
C111—C116—C115	120.5 (4)	H61C—C610—H61D	109.3
C111—C116—H116	119.7	C612—C611—C610	101.9
C115—C116—H116	119.7	C612—C611—H61E	111.4
C122—C121—C126	118.8 (4)	C610—C611—H61E	111.4
C122—C121—P	121.6 (3)	C612—C611—H61F	111.4
C126—C121—P	119.6 (3)	C610—C611—H61F	111.4
C121—C122—C123	121.1 (4)	H61E—C611—H61F	109.3
C121—C122—H122	119.5	O63—C612—C611	106.7
C123—C122—H122	119.5	O63—C612—H61G	110.4
C124—C123—C122	119.2 (5)	C611—C612—H61G	110.4
C124—C123—H123	120.4	O63—C612—H61H	110.4
C122—C123—H123	120.4	C611—C612—H61H	110.4
C123—C124—C125	120.8 (5)	H61G—C612—H61H	108.6
Pd—O41—C41—O42	−173.2 (3)	C47—C46—C42—C43	−177.7 (6)
Pd—O41—C41—C42	6.0 (5)	C42—C43—C44—C45	−2.5 (8)
O41—C41—C42—C43	141.3 (4)	C41—C42—C47—S	6.8 (6)
O41—C41—C42—C47	−41.5 (6)	C42—C47—S—C51	−67.5 (4)
C41—C42—C43—C44	177.7 (5)